AU687022B2 - Amorphous solid modification of 2,2',2''-nitrilo(triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1 ,1'-biphenyl-2,2'-diyl)phosphite) - Google Patents

Amorphous solid modification of 2,2',2''-nitrilo(triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1 ,1'-biphenyl-2,2'-diyl)phosphite)

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AU687022B2
AU687022B2 AU56158/94A AU5615894A AU687022B2 AU 687022 B2 AU687022 B2 AU 687022B2 AU 56158/94 A AU56158/94 A AU 56158/94A AU 5615894 A AU5615894 A AU 5615894A AU 687022 B2 AU687022 B2 AU 687022B2
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tert
butyl
tris
tetra
phosphite
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AU5615894A (en
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Stephen D. Pastor
Sai P Shum
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The amorphous solid modification of 2,2',2''-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite] is obtained by melting said compound and rapidly cooling the melt. The amorphous solid is an effective process stabilizer for organic materials, especially polyolefins and particularly polypropylene.

Description

Amorphous Solid Modification of 2.2'.2"-Nitrilortriethyl-tris-(3.3'.5.5,-tetra-tert-butyl- 1.1 '-biphenyl-Σ^'-diyl) phosphite!
This invention pertains to an amorphous solid modification of 2,2',2"-nitrilo[triethyl-tris- (3,3',5,5'-tetra-tert-butyl-l,r-biphenyl-2,2'-diyl) phosphite], to a process for preparing said modification and the use thereof for stabilizing organic materials against oxidative, thermal or light-induced degradation.
2,2',2"-Nitrilo[tιiethyl-tris-(3>3',5,5'-tetra-tert-butyl-l,l'-biphenyl-2,2'-diyl) phosphite] is a compound having the formula I
This compound of formula I is useful as a processing stabilizer for organic materials as taught in US-A-4 318 845 and US-A-4374219. The compound of formula I is disclosed as being a white powder melting at 121-134°C. The relatively high melting point of the "white powder" form of the compound of formula I as disclosed in the above mentioned patents is a problem when stabilizing organic polymers processed at relatively low tempe¬ ratures such as blow molding of HDPE and processing of natural rubber. The result is the additive is not uniformly distributed within the organic polymer causing problems in the stabilization performance of the additive stabilizer.
In accordance with the present invention an amorphous form of the compound of formu- la I is obtained which does not suffer the problems associated with the higher melting powder reported previously. This new amorphous form is characterized by a glass transi¬ tion temperature (Tg) within the range of from 105-110°C free of any endothermic melting peak above 110°C up to 230°C as determined by differential scanning calorimetry (DSC). Additionally the amorphous form of the present invention gave a featureless X-ray diffrac¬ tion pattern obtained using Cu-Kα.
The instant invention also relates to a process for the preparation of this novel amorphous solid modification of the compound of formula I, which comprises melting said compound and rapidly cooling the melt
The preferred method consists of pouring the molten material onto a cool surface main¬ tained below 100°C, more preferably near 25°C. The amorphous solid thus obtained may be further ground or granulated into any desired particle size by conventional means.
The instant invention relates also to the amorphous solid form of 2-2',2"-nitrilo[triethyl- tris-(3,3'»5,5'-tetra-tert-butyl-l, -biphenyl-2,2'-diyl) phosphite], characterized by melting in the range of 105-110°C and by an X-ray diffraction pattern which is featureless, obtai¬ nable by melting said compound and rapidly cooling the melt
The amorphous solid according to the invention is highly suitable for stabilizing organic materials against oxidative, thermal or light-induced degradation.
Examples of such organic materials are:
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-l-ene, polyisoprene or polybutadiene, as well as poly¬ mers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods: a) radical polymerisation (normally under high pressure and at elevated temperature).
b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups JNb, Nb, Nib or NUT of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either π- or σ-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lTI) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, Ila and/or LLla of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Νatta), TΝZ (DuPont), metallocene or single site catalysts (SSC).
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP LDPE) and mixtures of different types of polyethylene (for example LDPE HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl mono¬ mers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but- 1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/- isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon mon¬ oxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpoly- mers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethy- lidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE ethylene- vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon mon¬ oxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).
6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene buta- diene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copoly¬ mers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/- propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/- styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/- propylene/ styrene.
7. Graft copolymers of styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on. polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate buta- diene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epi- chlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from α,β-unsaturated acids and derivatives thereof such as polyacry- lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylo- nitriles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/- alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, poly¬ vinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, poly¬ ethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with sty¬ rene polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybuta- dienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, poly¬ amide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or graf¬ ted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-l,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.
22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.
25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins derived from polyepoxides, for example from bisglycidyl ethers or from cycloaliphatic diepoxides.
27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homolo¬ gous derivatives thereof, for example cellulose acetates, cellulose propionates and cellu- lose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
28. Blends of the aforementioned polymers (polyblends), for example PP EPDM, Poly- amide/EPDM or ABS, PVC/EVA, PVQABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PNC/CPE, PVC acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA PPO.
29. Naturally occurring and synthetic organic materials which are pure monomeric com¬ pounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adi- pates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emul¬ sions of such materials.
30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.
Accordingly, the invention also relates to compositions comprising (a) an organic material subjected to oxidative, thermal or light-induced degradation and (b) the amorphous solid form of 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-l,l '-biphenyl-2,2'-diyl) phos¬ phite].
Preferably, the organic materials to be protected are natural, semi-synthetic or, preferably, synthetic organic materials. Particular preference is given to thermoplastic polymers, in particular PVC or polyolefins, especially polyethylene and polypropylene.
The action of the compounds according to the invention against thermal and oxidative de¬ gradation, especially under thermal stress, such as occurs during processing of thermoplas¬ tics, may be mentioned in particular. Accordingly, the compounds according to the inven¬ tion are highly suitable for use as processing stabilizers.
Preferably, the amorphous solid form of 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-bu- tyl-l,l'-biphenyl-2,2'-diyl) phosphite] according to the invention is added to the material to be stabilized in amounts of 0.01 to 10%, for example 0.01 to 5%, preferably 0.05 to 3%, in particular 0.05 to 1%, relative to the weight of the organic material to be stabilized.
The compositions according to the invention can contain, in addition to the amorphous solid form of 2,2\2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-l,l'-biphenyl-2,2'-diyl) phosphite], further co-stabilizers, for example the following:
1. Antioxidants
1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl- 4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclo- hexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6Tdi-nonyl-4-methylphenol, 2,4-dimethyl-6- ( 1 '-methylundec- 1 '-yl)phenol, 2,4-dimethyl-6-( 1 -methylheptadec- 1 '-yl)phenol, 2,4-di- methyl-6-(r-methyltridec-r-yl)phenol and mixtures thereof.
1.2. Alkylthiomethylphenols. for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-do- decylthiomethyl-4-nonylphenol.
1.3. Hydroquinones and alkylated hydroquinones. for example 2,6-di-tert-butyl-4- methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-di- phenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxy- anisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
1.4. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tert-butyl-4-methyl- phenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thio- bis(6-tert-butyl-2-methylphenol), 4,4'-thiobis-(3,6-di-sec-amylphenol), 4,4'-bis-(2,6-dim- ethyl-4-hydroxyphenyl) disulfide.
1.5. Alkylidenebisphenols, for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methyl- cyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylene- bis(6-nonyl-4-methylphenol), 2,2' -methylenebis(4,6-di-tert-butylphenol), 2,2' -ethylidene- bis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methy- lenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)- 4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert- butyl-2-methylphenol), 1 , l-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3- tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1 , 1 ,3-tris(5-tert-butyl-4-hydroxy- 2-methylphenyl)butane, l,l-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmer- captobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3- tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy- 5 ' -methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1 , 1 -bis-(3,5-dimethyl-2- hydroxyphenyl)butane, 2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5- tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1 , 1 ,5,5-tetra-(5-tert- butyl-4-hydroxy2-methylphenyl)pentane.
1.6. O-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4,-dihydroxy- dibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tris-(3,5-di-tert- butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithio- terephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5di-tert-butyl-4- hydroxybenzylmercaptoacetate.
1.7. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2- hydroxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malo- nate, di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis- [4-(l,l,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
1.8. Aromatic hydroxybenzyl compounds, for example l,3,5-tris-(3,5-di-tert-butyl-4-hy- droxybenzyl)-2,4,6-trimethylbenzene, l,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6- tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
1.9. Triazine Compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4- hydroxyanilino)- 1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxy- anilino)-l,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)- 1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-l,2,3-triazine, 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, l,3,5-tris(4-tert-butyl-3-hydroxy-2,6-di- methylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)- 1 ,3,5-tri- azine, l,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-l,3,5-triazine, l,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate. 1.10. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphos- phonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecy ,5-di-tert- butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzyl- phosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzyl- phosphonic acid.
1.11. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.12. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or poly¬ hydric alcohols, e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hy- droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri- methylolpropane, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.13. Esters of β-(5-tert-butyl-4-hvdroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonane- diol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis- (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri- methylolpropane, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.14 Esters of β-(3,5-dicyclohexyl-4-hvdroxyphenyl)propionic acid with mono- or poly¬ hydric alcohols, e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hy- droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri- methylolpropane, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.15 Esters of 3,5-di-tert-butyl-4-hvdroxyphenyl acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethy¬ lene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxy- ethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpro- pane, 4-hydroxymethyl- 1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.16. Amides of β-(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di- tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3,5-di-tert-butyl- 4-hydroxyphenylpropionyl)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxy- phenylpropionyl)hydrazine.
2. UV absorbers and light stabilisers
2.1. 2-(2'-Hvdroxyphenyl)benzotriazoles, for example 2-(2'-hydroxy-5'-methylphenyl)- benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'- hydroxyphenyl)benzotriazole, 2-(2' -hydroxy-5' -( 1 , 1 ,3,3-tetramethylbutyl)phenyl)benzo- triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl- 2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'- hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'- di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis-(α,α-dimethylbenzyl)-2'- hydroxyphenyl)benzotriazole, mixture of 2-(3,-tert-butyl-2'-hydroxy-5'-(2-octyloxycar- bonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-car- bonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5 -(2- methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5,-(2- methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5,-(2-octyl- oxycarbonylethyl)phenyl)benzotriazole, 2-(3,-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonyl- ethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5,-methylphenyl)benzo- triazole, and 2-(3,-tert-butyl-2,-hydroxy-5,-(2-isooctyloxycarbonylethyl)phenylbenzotri- azole, 2,2'-methylene-bis[4-( 1 , 1 ,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol] ; the transesterification product of 2-[3,-tert-butyl-5,-(2-methoxycarbonylethyl)-2'-hydroxy- phenyl]-2H-benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO(CH2)3-]5- , where R = 3,-tert-butyl-4,-hydroxy-5,-2H-benzotriazol-2-ylphenyl.
2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-de- cyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids, as for example 4-tertbutyl- phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4- tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tertbutylphenyl 3,5-di-tert-butyl- 4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert- butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxy- benzoate.
2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-di- phenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxy- cinnamate, butyl α-cyano-β-methyl-p-methoxy-cinnamate, methyl α-carbomethoxy-p- methoxycinnamate and N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis-[4-(l,l,3,3-tetra- methylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldi- thiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4- hydroxy-3,5-di-tert-butylbenzylphosphonic acjd, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of l-phenyl-4-lauroyl-5- hydroxypyrazole, with or without additional ligands.
2.6. Stericallv hindered amines, for example bis(2,2,6,6-tetramethyl-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-piperidyl)succinate, bis( 1 ,2,2,6,6-pentamethylpiperidyl)sebacate, bis(l,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of l-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succi- nic acid, the condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenedi- amine and 4-tert-octylamino-2,6-dichloro-l,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperi- dyl) nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4- piperidyl)-l,2,3,4-butane-tetracar- boxylate, 1, 1 '-(l,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6- tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(l,2,2,6,6-penta- methylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl- 7,7,9,9-tetramethyl-l,3,8-triazasprio[4.5]decan-2,4-dion, bis(l-octyloxy-2,2,6,6-tetra- methylpiperidyl)sebacate, bis(l-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, the condensate of N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-l,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n-butyl- amino-2,2,6,6-tetramethylpiperidyl )-l,3,5-triazine and l,2-bis(3-aminopropylamino)- ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-l,2,2,6,6-pentamethylpiperi- dyl)-l,3,5-triazine and l,2-bis-(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9- tetramethyl-l,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl- 1- (2,2,6,6- tetramethyl-4- piperidyl)pyrrolidin-2,5-dione, 3-dodecyl-l-(l,2,2,6,6-pentamethyl-4-piperidyl)pyrroli- dine-2,5-dione. 2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butox- anilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethoxanilide, N,N'- bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mix¬ ture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and mixtures of ortho- and para- methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxani- lides.
2.8. 2-(2-Hvdroxyphenyl)-l,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxy- phenyl)-l,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-l,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)- 1 ,3,5-triazine, 2-(2-hy- droxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-dodecyl- oxyphenyl)-4,6-bis(2,4-dimethylphenyl)-l,3,5-triazine, 2-[2-hydroxy-4-(2hydroxy- 3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-l,3,5-triazine, 2-[2-hydroxy-4-(2- hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-l,3,5-triazine.
3. Metal deactivators, for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl) hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl- propionyl) hydrazine , 3-salicyloylamino-l,2,4-triazole, bis(benzylidene)oxalyl di- hydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-di- acetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)- thiopropionyl dihydrazide.
4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phos¬ phites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, triocta- decyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phos¬ phite, dϋsodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaeryt hritol diphosphite, diisode- cyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol di¬ phosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphsophite, tristearyl sorbitol tri- phosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 6-isooctyl- oxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-l,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10- tetra-tert-butyl- 12-methyl-dibenz[d,g]- 1 ,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6- methylphenyl)methylphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite. 5. Peroxide scavengers, for example esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, penta¬ erythritol tetrakis(β-dodecylmercapto)propionate.
6. Polyamide stabilisers, for example, copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
7. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, tri- allyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyure¬ thanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium rici- noleate and potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate.
8. Nucleating agents, for example, 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.
9. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
10. Other additives, for example, plasticisers, lubricants, emulsifiers, pigments, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
11. Benzofuranones and indolinones. for example those disclosed in US-A-4325 863, US-A-4 338 244 or US-A-5 175 312, or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl- benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-bu- tyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert- butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofu- ran-2-one.
The co-stabilizers, with the exception of the benzofuranones listed under 11, are added for example in concentrations of 0.01 to 10%, relative to the total weight of the material to be stabilized. Further preferred compositions comprise, in addition to components (a) and (b) further additives, in particular phenolic antioxidants, light stabilizers or processing stabilizers.
Particularly preferred additives are phenolic antioxidants (item 1 of the list), sterically hin¬ dered amines (item 2.6 of the list), phosphites and phosphonites (item 4 of the list) and peroxide-destroying compounds (item 5.) of the list.
Additional additives (stabilizers) which are also particularly preferred are benzofuran-2- ones, such as described, for example, in US-A-4325 863, US-A-4338 244 or US-A-5 175 312.
Examples of such benzofuran-2-ones are compounds of the formula
in which
Rπ is phenyl or phenyl which is substituted by 1 to 3 alkyl radicals together having at most 18 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkoxycarbonyl having 2 to 18 carbon atoms or chlorine;
R12 is hydrogen;
R14 is hydrogen, alkyl having 1 to 12 carbon atoms, cyclopentyl, cyclohexyl or chlorine;
R13 has the meaning of R12 or R14 or is a radical of the formula ,
O O O O
II II >ι π
— (CH2)n-C-NR18-A-NR18-C-(CH2)n-E ' — (CH2)n-C-NR18-A-O-C-(CH2)n-E .
-D-E, in which
R16 is hydrogen, alkyl having 1 to 18 carbon atoms, alkyl having 2 to 18 carbon atoms which is interrupted by oxygen or sulfur, dialkylaminoalkyl having a total of 3 to 16 carbon atoms, cyclopentyl, cyclohexyl, phenyl or phenyl which is substituted by 1 to 3 alkyl radicals together having at most 18 carbon atoms; n is 0, 1 or 2; the substituents R17, independently of one another, are hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl which is substituted by 1 or 2 alkyl radicals together having at most 16 carbon atoms, a radical of the formula -C2H4OH,
O
II
-C2H4-O-CmH2m+ι or -C2H4-O-C-R20 or together with the nitrogen atom to which they are attached form a piperidine or morpholine radical; m is 1 to 18;
R2o is hydrogen, alkyl having 1 to 22 carbon atoms or cycloalkyl having 5 to 12 carbon atoms;
A is alkylene having 2 to 22 carbon atoms which may be interrupted by nitrogen, oxygen or sulfur;
R18 is hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl which is substituted by 1 or 2 alkyl radicals together having at most 16 carbon atoms, or is benzyl;
R19 is alkyl having 1 to 18 carbon atoms;
D is -O-, -S-, -SO-, -SO2- or -C(R21)2- ; the substituents R21, independently of one another, are hydrogen, Cj--C16alkyl, the two R2χ together containing 1 to 16 carbon atoms, R2} is furthermore phenyl or a radical of the
formula , in which n, R16 and R17 are as defined above;
E is a radical of the formula
in which Rπ, R12 and R14 are as defined above; and
R15 is hydrogen, alkyl having 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, chlorine or a
O P radical of the formula -CH2-C-OR16 or -CH2-C-N(R17)2 , in which R16 and R17 are as defined above, or R15 together with R14 forms a tetramethylene radical.
Preference is given to those benzofuran-2-ones in which R13 is hydrogen, alkyl having 1 to 12 carbon atoms, cyclopentyl, cyclohexyl, chlorine or a radical of the formula
— (CH2)^*!-C-OR16 , — (CH2 *) —Λ C-N(R17)2 or -D-E> in hich n» Ri6> Rπ> D and E are as defined above, R16 is in particular hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl or cyclohexyl.
Preference is given furthermore to those benzofuran-2-ones in which Rπ is phenyl or phenyl which is substituted by 1 or 2 alkyl radicals together having at most 12 carbon atoms; R12 is hydrogen; R14 is hydrogen or alkyl having 1 to 12 carbon atoms; R13 is
hydrogen, alkyl having 1 to 12 carbon atoms, ,
or -D-E; R15 is hydrogen, alkyl having 1 to 20 carbon atoms,
-CH2 ,--CC--ιOR16 or , or R15 together with R14 forms a tetramethylene radical, n, R16, R17, D and E being as defined at the beginning.
Of particular interest are also those benzofuran-2-ones in which Rn is phenyl; R13 is hydrogen, alkyl having 1 to 12 carbon atoms or -D-E; R12 and R14, independently of one another, are hydrogen or alkyl having 1 to 4 carbon atoms; and R15 is alkyl having 1 to 20 carbon atoms, D and E being as defined at the beginning.
Of special interest are finally also those benzofuran-2-ones in which Rπ is phenyl; R13 is alkyl having 1 to 4 carbon atoms or -D-E; R12 and R14 are hydrogen; and R15 is alkyl having 1 to 4 carbon atoms, cyclopentyl or cyclohexyl, D being a group -C(R2ι)2- and E being a radical of the formula
the substituents R2ι being identical to or different from one another and each being alkyl having 1 to 4 carbon atoms, and Rπ, R12, R14 and R15 being as defined.
The amount of additional additives, in particular stabilizers, for example of the benzofu- ran-2-ones mentioned, can vary within wide limits. For example, 0.0005 to 10, preferably 0.001 to 5, in particular 0.01 to 2, % by weight thereof can be present in the compositions according to the invention.
Incorporation of the amorphous solid form of 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra- tert-butyl-l,l'-biphenyl-2,2'-diyl) phosphite] and, if desired, further additives in the poly¬ mer organic material is carried out by known methods, for example before or during moul¬ ding or by applying the dissolved or dispersed compounds to the polymer organic mate¬ rial, if appropriate with subsequent slow evaporation of the solvent. The amorphous solid modification according to the invention can also be added to the materials to be stabilized in the form of a masterbatch containing them, for example, in a concentration of 2.5 to 25% by weight.
The amorphous solid modification according to the invention can also be added before or during polymerization or before crosslinking.
The amorphous solid modification according to the invention can be incorporated in the material to be stabilized in pure form or encapsulated in waxes, oils or polymers. The amorphous solid modification according to the invention can also be sprayed onto the polymer to be stabilized. They are capable of diluting other additives (for example the abovementioned customary additives) or their melts, thus enabling them to be sprayed onto the polymer to be stabilized also together with these additives. Addition by spraying during deactivation of the polymerization catalysts is particularly advantageous, it being possible, for example, for the steam used for deactivation to be used for spraying.
In the case of bead polymerized polyolefins, it may be advantageous, for example, to apply the amorphous solid modification according to the invention, if desired together with other additives, by spraying.
The materials thus stabilized can be used in a wide range of forms, for example as films, fibres, tapes, moulding compositions, profiles or as binders for paints, adhesives or ce¬ ments.
As already mentioned, the organic materials to be protected are preferably organic, in par¬ ticular synthetic, polymers. Of these, the materials being protected are particularly advan¬ tageously thermoplastic materials, in particular polyolefins. The excellent efficiency of the amorphous solid form of 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-l, -biphe- nyl-2,2'-diyl) phosphite] as processing stabilizer (thermal stabilizer) should be mentioned in particular. To this end, it is advantageously added to the polymer before or during its processing. It is however also possible to stabilize other polymers (for example elasto¬ mers) or lubricants or hydraulic fluids against degradation, for example light-induced or thermal-oxidative degradation. For elastomers, see the above list of possible organic mate¬ rials.
Suitable lubricants and hydraulic fluids are based, for example, on mineral or synthetic oils or mixtures thereof. Lubricants are known to one skilled in the art and described in the relevant technical literature, for example in Dieter Klamann, "Schmierstoffe und ver- wandte Produkte" (Verlag Chemie, Weinheim 1982), in Schewe-Kobek, "Das Schmier- mittel-Taschenbuch" (Dr. Alfred Hϋthig- Verlag, Heidelberg, 1974) and in "Ullmanns EnzyklopSdie der technischen Chemie" vol. 13, pages 85-94 (Verlag Chemie, Weinheim, 1977).
Accordingly, a preferred embodiment of the present invention is the use of the amorphous solid form of 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-l,l'-biphenyl-2,2'-diyl) phosphite] for stabilizing organic materials against oxidative, thermal or light-induced de¬ gradation.
The amorphous solid modification according to the invention is preferably used as proces¬ sing stabilizer (thermal stabilizer) of thermoplastic polymers.
The present invention also provides a process for stabilizing an organic material against oxidative, thermal or light-induced degradation, which comprises incorporating therein or applying thereto the amorphous solid form of 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra- tert-butyl-l,l'-biphenyl-2,2'-diyl) phosphite].
The instant amorphous form of 2,2',2"-mtrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-l,r- biphenyl-2,2'-diyl) phosphite] shows a faster rate of dissolving and better solubility in or¬ ganic materials, such as in polymers and in lubricants, as compared to the prior art crystal¬ line form. This provides better compatibility and more uniform distribution of the instant amorphous form of 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-l, -biphenyl- 2,2'-diyl) phosphite] with an organic polymer during formulation compared to the prior art compound melting at 121-134°C.
Differential scanning calorimetry (DSC) measurements are obtained on a TA Instrument Inc., 910 differential scanning calorimeter, with a 100 ml/min nitrogen purge, aligned alu¬ minum pan, temperature scan at 5°C/min to 230°C.
X-ray diffraction patterns are recorded on a Philips Norelco X-ray Diffractometer unit, using Cu-Kα radiation with a nickel filter.
The examples which follow further illustrate the invention. The parts or percentages given are by weight.
Example 1:
The compound of formula 1, 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-l,l'-bi- phenyl-2,2'-diyl) phosphite], is prepared according to procedure of Example 4 of U.S. Patent No. 4,318,845. The compound of formula I is heated at 210°C until a clear melt is obtained. The melt is cooled rapidly to ambient temperature to yield a glassy solid with a Tg(DSC) of 105°-110°C. The white solid is conveniently ground into a white powder using a mortar and pestle. The X-ray diffraction pattern obtained using Cu-Kα is feature¬ less. Analysis: Calcd for C9oH132NO9P3: C, 73.8; H, 9.1; N, 0.96 %. Found: C, 73.4; H, 9.3; N, 0.9 %.
Example 2: Bulk Density
This example illustrates the superior packaging properties of the novel amorphous solid modification of the compound of formula I as prepared in Example 1 as compared to the powder form of the compound of Example 4 of U.S. Patent No. 4,318,845.
The apparent bulk density of the solids is measured according to the method of ASTM D-1895 (79). A higher apparent bulk density allows for a greater mass per unit volume which affords advantages in packaging of the solid product, such as lower costs for the packaging material, less storage space is required, etc. The results are listed in Table 1.
Table 1:
Example 3: Process Stabilization of Polypropylene at 274°C.
The base formulation comprises unstabilized, high yield/high selectivity catalyzed poly¬ propylene (PROFAX® 6501, Batch No. BD07155, produced by Himont) containing 0.075% by weight of calcium stearate. The test additives are incorporated into the poly¬ propylene by dry blending or, when the additive is a liquid, using a minimum amount of methylerie chloride solvent. The solvent is then removed by evaporation under reduced pressure. The stabilized resin formulation is extruded at 90 rpm from a 2.54 cm diameter extruder at 274°C with a residence time of 90 seconds. After each of the first, third and fifth extrusions, the melt flow rate (in grams/10 minutes) is determined by ASTM method D1238 on the pellets obtained from the extruder. The melt flow rate is a measure of the molecular weight of the polymer and indicates whether thermal degradation is occurring during melt processing by extrusion. A minimum change in melt flow rate is favored and indicates good melt processing stabilization. A substantial increase in the melt flow de¬ notes pronounced chain degradation, i.e. poor stabilization.The results are given in Table 2 below.
Table 2:
AO A is neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate).
Example 4: Solubility of amorphous solid form (Example 1, Compound A) and crystalline compound of formula I (Example 4 of US-A-4318 845, m.p. 121-134°C, Compound B) in Mobil BB® oil. Both compounds have the same uniform particle sizes (40-70 micron).
a) Into a vial of 980 mg of Mobil BB® oil was added 20 mg of compound A at ambient temperature. For the first 30 minutes, the vial was shaken every 10 minutes. After the ini¬ tial 30 minutes, the vial was left standing. All of compound A dissolved into the oil after 2.5 hours to give a clear solution.
b) Into a vial of 980 mg of Mobil BB® oil was added 20 mg of compound B at ambient temperature. For the first 30 minutes, the vial was shaken every 10 minutes. After the ini- tial 30 minutes, the vial was left standing. After 2.5 hours, compound B gave a cloudy sus¬ pension. A clear solution was obtained after 16 hours.
c) Into a vial of 980 mg of Mobil BB® oil was added 20 mg of compound A at ambient temperature. The vial was then placed into a 60°C oil bath. After 10 minutes, all of com¬ pound A dissolved into the oil to give a clear solution.
d) Into a vial of 980 mg of Mobil BB® oil was added 20 mg of compound B at ambient temperature. The vial was then placed into a 60°C oil bath. After 10 minutes, compound B gave a cloudy suspension. A clear solution was obtained after 16 hours.
e) Into a vial of 980 mg of Mobil BB® oil was added 10 mg of compound A at ambient temperature. For the first 30 minutes, the vial was shaken every 10 minutes. After the ini¬ tial 30 minutes, the vial was left standing. All of compound A dissolved into the oil after 1.5 hours to give a clear solution.
f) Into a vial of 980 mg of Mobil BB® oil was added 10 mg of compound B at ambient temperature. For the first 30 minutes, the vial was shaken every 10 minutes. After the ini¬ tial 30 minutes, the vial was left standing. After 1.5 hours, the mixture was a cloudy sus¬ pension. A clear solution was obtained after 16 hours.
A faster rate of dissolving a stabilizer in an oil results in a better compatibility and more uniform distribution of the stabilizer in an organic polymer during formulation. The results are summarized in Table 3.
Table 3:
a) The temperature reading is the oil temperature. b) Clear solutions were obtained after 16 hours. c) Clear solution was obtained after 5 hours at 60°C. d) RT = room temperature.

Claims (16)

WHAT IS CLAIMED IS:
1. The amorphous solid form of 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-l,l'- biphenyl-2,2'-diyl) phosphite], characterized by melting in the range of 105-110°C and by an X-ray diffraction pattern which is featureless.
2. A process for the preparation of the amorphous solid form of the compound 2,2', 2"- nitrilo[triethyl-tris-(3,3 ' ,5,5'-tetra-tert-butyl- 1 , 1 '-biphenyl-2,2'-diyl) phosphite] which comprises melting said compound and rapidly cooling the melt.
3. A process according to claim 2 which comprises pouring the molten material onto a cool surface maintained below 100°C.
4. A process according to claim 3 wherein the cool surface is near 25 °C.
5. The amorphous solid form of 2,2',2"-mtrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-l,r- biphenyl-2,2'-diyl) phosphite] obtainable by the process of claim 2.
6. A composition comprising a) an organic material subjected to oxidative, thermal or light-induced degradation, and b) the amorphous solid form of 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-bu- tyl- 1,1 '-biphenyl-2,2' -diyl) phosphite] as defined in claim 1 and 5.
7. A composition according to claim 6, additionally comprising, apart from components (a) and (b), further additives.
8. A composition according to claim 7, comprising, as further additives, phenolic antioxi¬ dants, light stabilizers or processing stabilizers.
9. A composition according to claim 7, comprising, as the further additive, at least one compound of benzofuran-2-one type.
10. A composition according to claim 6, comprising, as component (a), natural, semi-syn¬ thetic or synthetic polymers.
11. A composition according to claim 6, comprising, as component (a), thermoplastic polymers.
12. A composition according to claim 6, comprising, as component (a), a polyolefin.
13. A composition according to claim 6, comprising, as component (a), polyethylene or polypropylene.
14. Use of the amorphous solid form of 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-bu- tyl-l,l'-biphenyl-2,2'-diyl) phosphite], as defined in claim 1 and 5, as stabilizer for orga¬ nic materials against oxidative, thermal or light-induced degradation.
15. Use according to claim 14, in which the amorphous solid form of 2,2',2"-nitrilo[tri- ethyl-tris-(3,3',5,5'-tetra-tert-butyl-l,r-biphenyl-2,2'-diyl) phosphite], as defined in claim 1 and 5, is used as processing stabilizer (thermal stabilizer) in thermoplastic polymers.
16. A process for stabilizing an organic material against oxidative, thermal or light-in¬ duced degradation, which comprises incorporating therein or applying thereto the amor¬ phous solid form of 2,2',2"-mtrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-l,l'-biphenyl- 2,2'-diyl) phosphite] as defined in claim 1 and 5.
AU56158/94A 1992-11-30 1993-11-22 Amorphous solid modification of 2,2',2''-nitrilo(triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1 ,1'-biphenyl-2,2'-diyl)phosphite) Ceased AU687022B2 (en)

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US07/983,186 US5276076A (en) 1992-11-30 1992-11-30 Amorphous solid modification of 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite]
US983186 1992-11-30
PCT/US1993/011326 WO1994012506A1 (en) 1992-11-30 1993-11-22 Amorphous solid modification of 2,2',2''-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite]

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